Production of sulfonic acids of aliphatic and hydroaromatic carboxylic acids



' which are sulfuric Patented Sph 12, 1933 V UNITED STATES PATENT I OFFICE l PRODUCTION OF SULFONIO ACIDS 0F ALIPHA'IIC AND ROAEOMATNI BOX YLIC AC8 Fritz Giinther and Josef Hetzer, Ludwigshafenon-the-Rhine, Germany, assignors to I. G. Farbenindustrie Aktienges'ellschafc, it- Main, Ge, a corporation of Ge 1, it

No'Drawing. firiginal application June '3, 1927,

Serial No. 197,;223, and in Go 1926. Divided and this application- 1928. Serial No. 269,023

energetic c nditions. That means that either stronger s onating agents than sulfuric acid such as sulfuric acid anhydride, fuming sulfuri acid, or chloros'ulfonic acid should be employed, at room temperature or elevated temperatures, or

when using concentrated sulfuric acid, the treat-- ment should be carried out at temperatures of at least 100 C. The action of the sulfonating agents may take place either in the presence or absence of diluting media which are not sulfonated under the conditions of working, such'as .nitrobenzene, or carbon tetrachlorid, or of catalysts, for example phosphoric anhydride, diatomaceousearth, active carbon and the like, or both.

The sulfonic true sulfonic acids containing the group in contradistinction to ,the so-called aliphatic and hydroaromatic sulfonic acids hitherto known acid esters and contain the group 7 v and alsothe salts of the iiew sulfonic acids are excellent wetting, emulsifying, cleansing and dissolving agents for a great variety of substances and arealso excellently suitable for use as fat saponifiers. The new sulfonic acids and sulfonic acid salts are soluble in water and many organic liquids and produce solutions having in high de'-' gree the properties of giving lather, of wetting and emulsifying. They are very stable against the action of halogen. Above all they possess the property of-hot being decomposed by acidsand compounds differfrom Turkey red oils and similar.

suliuricaddesters, 1

acids thus obtained, which are- June 9,

April 10 The new\pr oducts can also be employed for the production of clear aqueous solutions of or ganic substances which are insoluble or not miscible with water, such as hydrocarbons, water-insoluble alcohols, ketonec, esters and other insoluble or difllcultly soluble organic compounds, for example of benzene, tetrahydronaphthalene, petroleum hydrocarbons, butyl or amyl alcohols, cyclohexanol, cyclohexanone and the like. The ammonium salts of the sulfonic acids are especially suitable for this purpose.

In order to obtain such clear (probably colloidal) solutions, rather definite proportions of the ingredients must be employed, which proportions vary according to the nature of the sulfonic acid or sulfonic acid salt employed and of the organic substance to be dissolved and can readily beascertained by some tests. For example, a' clear solution is obtained by mixing 5 parts. by weight, of cyclohexanol with 10 parts, by weight, of an' aqueous solution of mono-sodium sulfo-oleate containing about 27 per cent of carbon which corresponds to about 5 parts, by weight, of the said salt. The clear solutions thus obtained canfrom the solutions for example by diluting with water. v o

The sulionic acids according to the present I invention, insofar as they are derived from carboxylic acids of aliphatic hydrocarbons of -coniparatively low molecular weight, can be ,made

more suitable for the said purposes of application,

ionic acids of aliphatic carboxylic acids is'also often. advantageous when the latter have a comparatively high molecular weight. g Suitable inltial'materials for the production of the new compounds are for example oleic,

'stearic, palmitic acids or esters thereof with monoor polyvalent alcohpls such as myricil alcohol or glycerol, octohydro-anthracene and the like. V I

The following examples will further illustrate how our invention may be carried out in practice, but the invention is not limited to these examples. The parts are by weight.

. rmmme 1, 450' parts of chlorosulfonic acid are allowed stirring, into 142 parts of stearic acid. When the evolution of gas begins to cease, the mass is heated to about 100 C. After the sulfonation is complete, the reaction product which is now soluble in water, is poured into water, and filtered ofi, while hot, from the small amount of undissolved matter. On cooling, a gelatinous mass is obtained, which on dilution with water gives solutions possessing good lathering and wetting properties. 7

The reaction proceeds according to the equation I som- CuHnCO0H+ClS0;H HCl+CmHu-CH coon Aqueous solutions of the salts of the sulfonic acids thus obtained also possess strong soap-like properties. The alkali metal salts of the sulfonic acid-are for instance obtained by neutralization of the free acid with alkalies, but may also be produced by way of the intermediarily prepared calcium salt. Di1uents such as, for instance, carbon tetrachloride may also be present in the production of sulfonic acid. Oleic acid'may be analogously employed in the place of stearic acid.

Example 2 Molten palmitic acid is treated at about 100 C. while stirring, with sulfuric acid anhydride, until the reaction product becomes soluble in water. A syrupy product is thus obtained, which on cooling turns into a semi-solid mass, the acid, neutral or alkaline aqueous solutions of which have. excellent soap-like properties. The reaction procee'ds according to-the equation Example 3 Between 1 and 2 parts of the product obtained by the treatment of palmitic acid at 100 C. with sulfuric acid anhydride until the reaction product is soluble in water, are dissolved in 100 parts of water. A liquid capable of producinga very good lather is thus obtained, which wets wool,

cotton and. the like very rapidly. and efl'ectively.

The sulfonic acids obtained from stearic acid ormixtures of stearic acid and palmitic acid may be employed in the same way.- The neutral or alkaline solutions of the said sulfonic acids also possess excellent wetting properties.

Example 4 282 parts of oleic acid arestirred with 300 parts of nitrobenzene and treated at about 5 to 10 C. with 160 parts of sulfur trioxid, for which about 5 to 6 hours are required.

The nitrobenz'ene is distilled off with steam and the product neutralized with alkali so that which can be employed in acid liquids as well it no longer shows acid reaction with con go- The reaction proceeds according to the equation:

K /R cm-wnm-cn-orr-(ormr-ooon An excellent wetting agent is thus obtained,

. as in neutral or alkaline solutions. Other unsaturated compounds such as the fatty acids of train oils, train oils themselves and the like may be employed in place of oleic acid.

What we claim is: 1. The process of producing sulfonic acids derived from non-aromatic hydrocarbon carboxylic acids containing more than 8 carbon atoms in their molecule which comprises treating said nonaromatic hydrocarbon carboxylic acids with a sulfonating agent stronger than concentrated sulphuric acid at a temperature between room temperature and 100 C.

2. The process of producing sulfonic acids derived fromaliphatic saturated hydrocarbon carboxylic acids containing more than 8 carbon atoms in their molecule which comprises treating said aliphatic hydrocarbon carboxylic acids with a sulfonating agent stronger than concentrated sulphuricacid at a temperature between room temperature and 100 C. r 3. The compounds of manufacture a,-sulphonic acids of aliphatic saturated hydrocarbon carboxylic acids containing more than 8 carbon atoms in their molecule which contain the group coon are stable against acids and hard water, and possess good wetting and emulsifying properties.

4. The compound of manufacture palmitic sulphonic acid which contains the group SOiOH =C V ooon is stable against acids and hard water, and possesses good wetting and emulsifyin properties. 5. The process of producing a true sulionic acid which comprisestreating a fatty acid selected from the class consisting of palmitic and staric acids at a temperature rangin from room temperature to 100 C. with a sulfonating agent selected from the class consisting of chlorosultonic acid, fuming sulfuric acid, and sulfuric acid anhydride. v FRITZ GfiNTHER.

JOSEF HETZER. 

